Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C255/00—Carboxylic acid nitriles
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
  • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids

Definitions

• the invention relates to novel 1,10-substituted 10-amino-deca-3,7-diene-nitriles and also to a process for their preparation.
• the novel 10-amino-deca-3,7-diene-nitriles are valuable starting materials for the preparation of corresponding 1,11-diamino-undeca-3,7-dienes, which in turn are applied, for example, as polycondensation components, in particular for the preparation of crosslinkable polyamides.
• novel 1,10-substituted 10-amino-deca-3,7-diene-nitriles are those of the formula I ##STR2## in which R 1 is alkyl having 1-12 C atoms, R 2 is hydrogen or alkyl having 1-12 C atoms, R 3 is alkyl having 1-12 C atoms, cycloalkyl having 4-12 ring C atoms, aralkyl having 7 or 8 C atoms, substituted or unsubstituted aryl or, if R 4 is hydrogen, --CH ⁇ CH--alkyl or --C(alkyl) ⁇ CH--alkyl each having 1-4 C atoms in the alkyl moieties, and R 4 is hydrogen, alkyl having 1-12 C atoms, cycloalkyl having 4-12 ring C atoms, aralkyl having 7 or 8 C atoms or substituted or unsubstituted aryl, or R 1 and R 2 and/or R 3 and R 4 together are alky
• Alkyl groups R 1 to R 4 can be straight-chain or branched. Alkyl groups R 1 , R 2 and R 4 preferably have 1-5 C atoms and are straight-chain. Alkyl groups R 3 advantageously have 1-7 C atoms and especially 1-5 C atoms. Examples of alkyl groups R 1 to R 4 are: the methyl, ethyl, n-propyl, isopropyl, n-, sec.- and tert.-butyl, n-pentyl, 2-pentyl or 3-pentyl, n-hexyl, 2-heptyl or 3-heptyl, n-octyl, n-decyl and n-dodecyl groups.
• R 3 is a group --CH ⁇ CH--alkyl or --C(alkyl) ⁇ CH--alkyl
• the alkyl groups in these substituents are preferably straight-chain and are especially methyl or ethyl.
• Cycloalkyl groups R 3 and R 4 can be unsubstituted or substituted by C 1-4 -alkyl groups. They are especially cycloalkyl substituted by a methyl or ethyl group.
• cycloalkyl groups R 3 and R 4 are unsubstituted and have 5-8 ring C atoms.
• the cyclopentyl group and, in particular, the cyclohexyl group are particularly preferred.
• Possible aralkyl groups R 3 and R 4 are, in particular, the benzyl, methylbenzyl or phenylethyl group. If R 3 or R 4 is substituted aryl, possible substituents are, in particular, alkyl groups having 1-4 and especially 1 or 2 C atoms.
• Aryl groups R 3 and R 4 can carry several alkyl groups, but are preferably substituted by only one alkyl group. Particular preferance is given to the 1-naphthyl or 2-naphthyl group, phenyl substituted by an alkyl group having 1-4 and particularly 1 or 2 C atoms, and, very particularly, unsubstituted phenyl.
• Alkylene groups represented by R 1 and R 2 and/or R 3 and R 4 together preferably have 4-7 C atoms. These are especially the tetramethylene group and, very particularly, the pentamethylene group.
• the compound of the formula I in which R 1 and R 2 are methyl, R 3 is isopropyl and R 4 is hydrogen is very particularly preferred.
• Examples of specific compounds of the formula I are: 1,1-dimethyl-10-isopropyl-10-amino-deca-3,7-diene-nitrile, 1,1-dimethyl-10-methyl-10-amino-deca-3,7-diene-nitrile, 1,1-dimethyl-10-ethyl-10-amino-deca-3,7-dienenitrile, 1,1-dimethyl-10-n-hexyl-amino-deca-3,7-dienenitrile, 1,1-dimethyl-10-phenyl-amino-deca-3,7-diene-nitrile, 1,1-dimethyl-10-cyclohexyl-amino-deca-3,7-diene-nitrile, 1,1-diethyl-10-isopropyl-amino-deca-3,7-diene-nitrile, 1,1-diethyl-10-(3-pentyl)-amino-deca-3,7-diene
• the compounds of the formula I can be prepared by dehydrating compounds of the formula II ##STR3## in which R 1 , R 2 , R 3 and R 4 are as defined under the formula I.
• the dehydration of the compounds of the formula II can be carried out chemically or thermally, in a manner known per se.
• dehydrating agents for chemical dehydration are anhydrides of aliphatic monocarboxylic acids having 2-5 C atoms and unsubstituted or substituted by halogen atoms or alkyl groups, such as acetic, propionic, butyric and valeric anhydrides and trichloroacetic, trifluoroacetic, trimethylacetic, triethylacetic and tri-n-butylacetic anhydrides; alkyl chloroformates having 1-5 C atoms, such methyl, ethyl, isopropyl and isobutyl chloroformates; acetyl chloride, thionyl chloride, benzoyl chloride, benzenesulfonyl chloride, sulfuryl chloride, phosphorus pentoxide mixed with ethanol, phosphorus oxychloride, polyphosphoric acid and aqueous alkali, such as aqueous NaOH or KOH.
• the said dehydrating agents can, if appropriate, be used in a mixture with catalysts, for example alkaline earth metal or alkali metal salts of aromatic monocarboxylic acids or of aliphatic monocarboxylic acids having 1-3 C atoms, such as sodium benzoate, sodium salicylate, calcium and sodium formates, calcium, magnesium, sodium and potassium acetates and sodium propionate, or tertiary bases such as triethylamine, pyridine and dimethylaniline.
• catalysts for example alkaline earth metal or alkali metal salts of aromatic monocarboxylic acids or of aliphatic monocarboxylic acids having 1-3 C atoms, such as sodium benzoate, sodium salicylate, calcium and sodium formates, calcium, magnesium, sodium and potassium acetates and sodium propionate, or tertiary bases such as triethylamine, pyridine and dimethylaniline.
• the preferred dehydrating agent is acetic anhydride.
• Chemical dehydration is advantageously carried out in the presence of an organic diluent or solvent which is inert under the reaction conditions.
• suitable diluents or solvents are aromatic hydrocarbons such as benzene and toluene, aromatic or aliphatic nitriles, particularly benzonitrile and alkylnitriles having 2-5 C atoms, such as acetonitrile, propionitrile and butyronitrile, and also anhydrous acetic acid.
• Preferred diluents or solvents are acetonitrile and, in particular, anhydrous acetic acid.
• Chemical dehydration is generally carried out at temperatures of between 50° C. and the reflux temperature of the reaction mixture.
• Thermal dehydration can be carried out, for example, over aluminum oxide or thorium oxide at temperatures of between 340° and 360° C. Chemical dehydration is preferred.
• the starting materials of the formula II are known and can be prepared by the process described in European Pat. No. 11,599.
• the compounds of the formula I can be converted, for example by reduction, to correspondingly substituted 1,11-diamino-undeca-3,7-dienes of the formula III ##STR4## for example by means of Bouveault-Blanc reduction with sodium metal in alcohols, preferably isopropanol.
• R 1 to R 4 are as defined under the formula I.
• the diamines of the formula III are valuable intermediates and are applied, for example, as polycondensation components for the preparation of transparent crosslinkable polymers.
• Such polyamides can be prepared, in a manner known per se, by the polycondensation of diamines of the formula III with saturated or unsaturated aliphatic and/or aromatic dicarboxylic acids or amide-forming derivatives thereof, preferably in the presence of an inorganic or organic phosphorus compound as an accelerator. They can be crosslinked thermally or photochemically, preferably in the presence of free-radical initiators.
• Photochemical crosslinking is advantageously carried out by means of polythiols having at least two thiol groups per molecule, in the presence of photosensitisers such as benzophenone, thioxanthone and the like.
• photosensitisers such as benzophenone, thioxanthone and the like.
• the said polyamides or their mixtures with polythiols and sensitisers are suitable, for example, for the production of solvent-resistant coatings on various materials, particularly metals, for the production of images under the action of light or for the production of transparent mouldings, for example by the injection-moulding or extrusion process.
• the transparent polyamides obtained using diamines of the formula III and aromatic and/or aliphatic dicarboxylic acids, particularly terephthalic acid, isophthalic acid and/or adipic acid, are distinguished by low water uptake, high resistance to hydrolysis and/or good dimensional stability under the action of moisture. Furthermore, they give very strongly adhering, solvent-resistant coatings and, in contrast to previously known, unsaturated polyamides, have a good compatibility with polythiols. By virtue of their good solubility in various organic solvents, they can also be readily crosslinked under the action of heat.
• Mass spectrum molecular peak: 234, fragment masses: 205, 166, 82.
• Mass spectrum molecular peak: 268, fragment masses: 214, 146, 106, 79.
• Mass spectrum molecular peak: 220, fragment masses: 205, 190, 178, 98, 58.
• Mass spectrum molecular peak: 274, fragment masses: 259, 245, 191, 166, 112, 98.
• Mass spectrum molecular peak: 303, fragment masses 275, 233, 142, 100, 82.
• the coating is dried for 3 minutes at 100° C., after which the layer thickness is about 5 ⁇ m.
• Subsequent hardening at 150° C. for 90 minutes in a nitrogen atmosphere gives a hard, transparent and shiny layer with good adhesion to the copper. If the circuit board treated in this way is left to stand for 72 hours in chloroform at 60° C., the polyamide is not dissolved and the adhesion of the polyamide is sufficient to prevent etching of the underlying copper.
• the coating After storage for one week in water at 20° C., the coating retains its transparency and good adhesion to the copper; the water uptake is less than 1% by weight.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Polyamides (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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• 1983
  • 1983-01-24 EP EP83810028A patent/EP0085652B1/de not_active Expired
  • 1983-01-24 DE DE8383810028T patent/DE3360070D1/de not_active Expired
  • 1983-01-26 US US06/461,045 patent/US4472318A/en not_active Expired - Fee Related
  • 1983-01-27 CA CA000420349A patent/CA1192913A/en not_active Expired
  • 1983-01-27 JP JP58010636A patent/JPS58134068A/ja active Pending

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